O-alkyl-s-alkyl-s-phenyl-phosphorodithiolates

ABSTRACT

O-alkyl-S-alkyl-S-phenyl-phosphorodithiolates, i.e. O-alkyl-Salkyl-S-(optionally chloro and methyl -substituted)- phenyl- phosphorodithiolates or -dithiolphosphates, which possess fungicidal properties and which may be produced by conventional methods.

United States Patent 1 3,686,369 Hoffmann et a1. [45] Aug. 22, 1972 4]O-ALKYL-S-ALKYL-S-PHENYL- [56] References Cited PHOSPH ROD] [72] I t Lum t li w a1 El UNITED STATES PATENTS nve ors: e offmann, rt

Hans g have 3,322,864 5/1967 Schrader ..260/964 x kusen both of Germany;Toyohiko 3,444,274 5/1969 Schrader ..260/964 X Kume; Kazuomi Yasui, bothof FOREIGN PATENTS OR APPLICATIONS Tokyo-to, Japan 98,101 2/1964 Denmark..260/964 Asslgneei Fal'benfabnken Bayer Aktlen' 983,886 2/ 1965 GreatBritain ..260/964 gesellschaft, Leverkusen, Germany 22 Fl (11 I 1Primary Examiner-Joseph Rebold 1 1e Juy 969 Assistant ExaminerRichard L.Raymond [21] Appl. No.: 842,702 Attorney-Burgess, Dinklage and Sprung[30] Foreign Application Priority Data [57] ABSTRACTO-a1kyl-S-a1kyl-S-phenyl-phosphorodithiolates, i.e. O- Ju1y19, 1968Japan ..43/50851 alkyhspalkyksopfionany ch10) and methyl stituted)-phenyl- -phosphorodithio1ates or i "260/ dithiolphosphates, whichpossess fungicidal properties a n e n b d 58 Field of Search ..260/964and whlch may be produced y Come" me o s 11 Claims, No DrawingsO-ALKYL-S-ALKYL-S-PHENYL- PHGSPHORODITHIOLATES The present inventionrelates to and has for its objects the provision for particular newO-alkyl-S-alkyLS- phenyl-phosphorodithiolates, i.e. O-alkyl-S-alkyl-S-(optionally chloro and methyl -substituted)-phenylphosphorodithiolatesor -dithiolphosphates, which possess fungicidal properties, activecompositions in the form of mixtures of such compounds with solid andliquid dispersible carrier vehicles, and methods for producing suchcompounds and for using such compounds in a new way especially forcombating fungi, with other and further objects becoming apparent from astudy of the within specification and accompanying examples.

Heretofore, in controlling serious rice diseases such as blast andsheath blight, organic mercury compounds and organic arsenic compoundssuch as phenyl mercuric acetate, methyl arsonic acid, etc., whichcontain heavy metals harmful to man and cattle have been used widely,because they are excellent in their fungicidal effect and arecomparatively economical to use. However, the use of organic mercuriccompounds during the growing period of rice plants is objectionable froma public health standpoint because of the direct and indirect toxicityof these .known compounds to mammals, especially humans.

Accordingly, inexpensive and effective compounds which do not containany heavymetals harmful to man and cattle are urgently needed to combatrice diseases.

It has now been found, in accordance with the present invention, thatthe particular new O-alkyl-S- alkyl-S-phenyl-phosphorodithiolates of theformula in which R is alkyl of one-four carbon atoms,

R is branched chain alkyl of four-eight carbon atoms or straight chainalkyl of seven-eight carbon atoms, and

X is hydrogen, chloro or methyl, exhibit strong fungicidal properties.

It is already known that symmetric O,S-dialkyl-S-phenyl-phosphorodithiolates possess insecticidal properties. Forexample, O,S-diethyl-S-(4-chloro-phenyl)- phosphorodithiolate (A) andO,S-diethyl-S-phenylphosphorodithiolate (B) are disclosed as aninsecticide in German Pat. specification No. 1138041. An analogouscompound, O-n-butyl-S-ethyl-S-benzylphosphorodithiolate (C) is alsodisclosed as a fungicide and insecticide in Nederlandish Pat.specification No. 6806844.

In copending U.S. Application Ser. No. 830,513 filed June 3, 1969 nowabandoned, corresponding to Japanese Application Sho 41618/68 having apriority date of June 18, 1968, and of overlapping inventorshipherewith, certain O-lower alkyl(-cycloalkyl)-S-alkyl-S-phenyl-phosphorodithiolates are disclosed and claimed which possessfungicidal properties, i.e. O-n-butyl-S-methyl-S-(4-chloro-phenyl)-phosphorodithiolate andO-n-butyl-S-methyl-S-phenyl-phosphorodithiolate.

It has been furthermore found, in accordance with the present invention,that a process for the production of the compounds of formula (I) abovemay be provided, which comprises reacting anO-alkyl-S-alkylthiolphosphoryl halide of the formula in which R and Rare the same as defined above, and Hal is a halogen atom such as chloro,with a thiophenol or thiophenol salt of the formula III) in which X isthe same as defined above, and

M is hydrogen or alkali metal such as sodium.

Surprisingly, the particular new phosphorodithiolates of formula (I)above according to the present invention exhibit an excellent fungitoxiceffectiveness, especially for agricultural and horticultural purposes,more especially against rice diseases, and a certain insecticidaleffectiveness, with a comparatively low mammalian toxicity and aconcomitantly low phytotoxicity, whereas the known organic mercury andorganic arsenic compounds used for these purposes as aforesaid arehighly toxic to mammals. Therefore, the instant compounds represent avaluable contribution to the art.

The general process for the preparation of the instant compounds isillustrated by the following reaction scheme:

in which R, R, X, Hal and M are the same as defined above.

The starting materials to be used for producing the instant newcompounds are already known and are clearly characterized by theformulas (II) and (H1) noted above.

Advantageously, in accordance with the present invention, in the variousformulas herein:

R represents lower alkyl hydrocarbon of 1-4 carbon atoms such as methyl,I-4 and iso-propyl, n-, iso-, sec.- and tert.- butyl, and the like,especially C, or C alkyl;

R represents branched chain alkyl hydrocarbon of four-eight carbon atomssuch as iso-, sec.- and tert.-butyl, isoamyl (i.e. 3-methyl-butyl),sec.-amyl (i.e. 1- methyl-butyl), tert.-amyl (i.e. l,l-dimethylpropyl),iso-hexyl (i.e.4-methylpentyl), sec.-hexyl (i.e. l-methyl-pentyl),tert,-hexyl (i.e. 1,1- dimethylbutyl), iso-heptyl (i.e. S-methyl-hexyl),sec.-heptyl (i.e. l-methyl-hexyl), tert.-heptyl (i.e.1,1-dimethyl-pentyl), isooctyl (i.e. 6-methyl-heptyl), sec.-octyl (i.e.l-methyl-heptyl), tert.-octyl (i.e. 1,1-dimethyl-hexyl),1,3-dimethyl-butyl, 2- ethyl-butyl, 2,2-dimethyl-butyl,1,2,2-trimethylpropyl, 1,3-dimethyl-hexyl, 1,5-dimethyl-hexyl,2,3,4-tri-methyl-amyl, 3-ethyl-4-methyl-amyl, and the like, especiallyC,, or C branched chain alkyl, and more especially C., or C 4 branchedchain alkyl; or

straight chain alkyl hydrocarbon of seven-eight carbon atoms such asn-heptyl, n-octyl, and the like, especially n-octyl;

X represents hydrogen;

chloro; or

methyl;

X when chloro or methyl being in 2- 3- or 4- position, and especially in4- position;

Hal represents halo such as chloro, bromo, fluoro and iodo,,especiallychloro; and

M represents an alkali metal atom such as sodium, potassium, lithium,and the like, especially sodium and potassium.

Preferably, R is methyl, ethyl or nand, iso-propyl, R is a branchedchain alkyl of four-six carbon atoms, and X is hydrogen, methyl orchlorine.

As examples of thiolphosphoryl' halides of formula (H) above which maybe' used as starting materials, there are mentioned:O-iso-butyl-S-methyh O-isobutyl-S-ethyl-, O-sec-butyl-S-tnethylO-sec.-butyl-S- ethyl-, O-(1,3-dimethyl-butyl)-S-methyl,O-(i-methylhexyl)-S-ethyl-, O-(2-etl'iyl butyl)-S-methy1-, O-(2-ethyl-butyl)-S-ethyl-, O-(2,2-dirnethyl-butyl)-S- methyl-,O-(2,2-dimethyl-butyl)'- S-ethyl-, O-(1,2,2-trimethyl-propyl)-S-methyl-, O-( 1,2,2-trimethylpropyl)-S-ethyl-,O-iso-butyl-S-iso-propyl O-n-octyl- S-ethyl-, and the like,thiolphosphoryl chlorides, bromides, etc.

As examples of thiophenols and corresponding alkali metal salts offormula (III) above which may be used as starting materials, there arementioned: thiophenol, 2-, 3- and 4- chloro-thiophenol, 2-, 3- and 4-methyl-thiophenol, and the corresponding sodium and potassiumthiophenates, and the like.

The production process is preferably carried out in the presence ofinert solvents (the term solvent including mere diluents).

Suitable inert organic solvents usable for carrying out the productionprocess in this regard include hydrocarbons, such as benzene andbenzine; chlorinated hydrocarbons, such as methylene chloride, ethylenechloride, carbon tetrachloride and dichlorobenzene; ethers, such asdiethyl ether, dibutyl ether and dioxan; ketones, such as acetone,cyclohexanone and methylethyl ketone; and acetonitrile and dimethylformamide; and the like.

The reaction temperature can be varied within a fairly wide range. Ingeneral, the reaction is carried out at substantially betweenabout'O'l00C, preferably between about -80C.

A basic substance, preferably a tertiary amine, such as triethylamine,pyridine, dimethyl-cyclohexylamine, dimethylaniline,dimethylbenxylamine, and the like, is advantageously employed as acidbinding agent where the corresponding free starting thiophenol is used.

When carrying out the production process, approximately equimolaramounts of the starting reactants are used, but an excess of the acidbinding agent is not harmful, i.e. where the free thiophenol is used. Aninert organic solvent such as benzene may be employed and the reactionmay be carried out, for example, in triethylamine as acid binding agent,at a temperature of about 080C, by dissolving the thiophenol andtriethylamine in benzene and adding the thiolphosphoryl halide dropwisethereto.

After completion of the reaction (about 1-10 hours), the reactionmixture may be worked up in the usual manner, such as by washing thereaction mixture with water and thereafter with aqueous sodium carbonatesolution, then drying with anhydrous sodium sulfate, and distilling offthe benzene, The residue is in most cases a colorless or slightly yellowcolored non-distillable oil which is soluble in organic solvents andonly slightly soluble in water.

Advantageously, the particular new active compounds aceording to thepresent invention exhibit strong fungitoxic activity and aredistinguished by a broad spectrum of activity. Their low toxicity towarmblooded animals and their good compatibility with higher plantspermits the instant new compounds to be used as plant protection agentsagainst fungal plant diseases. In the concentration normally used forthe control of fungi, the instant compounds do not damage cultivatedplants.

Fungitoxic agents, such as the instantcompounds, are usable in plantprotection, i.e. agricultural and horticultural endeavors, for thecontrol of fungi from the most diverse classes of fungi, such asArchimycetes, Ascomycetes Phycomycetes, Basidiomycetes and FungiImperfecti.

The particular new active compounds according to the present inventioncan be used for example against parasitic fungi, on above-the-soil partsof plants, fungi which cause tracheomycosis which attack the plant fromthe soil, seedbome fungi and soil-inhabiting fungi.

By reason of their excellent properties mentioned above, the particularnew active compounds according to the present invention can also be usedwith good results against fungal diseases which hitherto had to becontrolled with fungicidal agents containing heavy metals harmful to manand cattle, e.g. arsenic and mercury.

The instant active compounds have given particularly good results in thecontrol of serious rice diseases including not only rice blast and brownspot, but also sheath blight. Thus, the instant compounds show anexcellent activity against the fungi Piricularia oryzae (i.e. blast),Cabhliobolus miyabeanus (i.e. brown spot) and Pellicularia sasakii (i.e.sheath blight), as well as against the fungi Mycosphaerella melonis(cucumber), Alternaria kikuchiana (pear), Elsinoe ampelina (grap and thelike.

In particular, the compounds of formula (I) above in which R is methyl,ethyl or nand iso-propyl, R" is a branched chain alkyl of four-sixcarbon atoms, and X is hydrogen, chloro or methyl, possess especiallymarked effect against serious rice diseases such as the aforesaid blast,brownspot and sheath blight.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert pesticidal diluents or extenders, i.e. inertconventional pesticidal dispersible carrier vehicles, to form solutions,emulsions, suspensions, emulsifiable concentrates, spray powders, oils,pastes, soluble powders, dusting agents, granules, tablets, etc. Theseare prepared in known manner, for instance by extending the activecompounds with conventional pesticidal dispersible liquid diluentcarriers and/or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g. conventional pesticidal surface-activeagents, including emulsifying agents and/or dispersing agents, whereby,for example, in the case where water is used as diluent, organicsolvents may be added as auxiliary solvents. The following may bechiefly considered for use as conventional carrier vehicles for thispurpose: inert dispersible liquid diluent carriers including inertorganic solvents and non-solvents, such as aromatic hydrocarbons (e.g.benzene, toluene, xylene, dimethyl napththalene, aromatic naphthas,etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g.chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), chlorinatedaliphatic hydrocarbons (e. g. methylene chloride, etc.), alcohols (e.g.methanol, ethanol, propanol, butanol, etc.), amines (e. g. ethanolamine,etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.),amides (e.g. dimethyl formamide, etc.), sulfoxidtw (e.g. dimethylsulfoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well asinert dispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate,talc, kieselguhr, diatomaceous earth, clay, montmorillonite, etc.), andground synthetic minerals (e.g. highly dispersed silicic acid,silicates, e.g. alkali silicates, etc. whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surface-active agents, for this purpose: emulsifying or wettingagents, such as non-ionic and/or anionic emulsifying or wetting agents(e.g. polyethylene oxide esters of fatty acids, polyethylene oxideethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., andespecially alkyl aryl-polyglycol ethers, magnesium stearate, sodiumoleate, etc); and/or dispersing agents, such as lignin, sulfite wasteliquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other fungicides, orherbicides, insecticides, acaricides, nematocides, bactericides, etc.,including, especially fungicidal, organophosphorus compounds, carbarnatecompounds, dithiocarbamate compounds, organo-chlorine compounds, dinitrocompounds, organic sulfur or copper compounds, substituted phenoxycompounds, chlorophenols, substituted diphenyl ethers, anilidecompounds, ureas, triazines, antibiotics, and other known agriculturalchemicals and/or fertilizers, if desired, or in the form of particulardosage preparations for specific application made therefrom, such assolutions, emulsions, suspensions, powders, pastes, and granules whichare thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95 percent, andpreferably 0.5- percent, by weight of the mixture, whereas carriercomposition mixtures suitable for direct application or fieldapplicationv generally contemplate those in which the active compound ispresent in an amount substantially between about 0.001-10 percent,preferably 0.0l5 percent, by weight of the mixture. Thus, the presentinvention contemplates over-all compositions which comprise mixtures ofa conventional dispersible carrier vehicle such as (1) a dispersibleinert finely divided carrier solid, and/or (2) a dispersible liquid suchas an inert organic solvent and/or water preferably including asurface-active effective amount of a carrier vehicle assistant, e.g. asurface-active agent, such as an emulsifying agent and/or a dispersingagent, and an amount of the active compound which is effective for thepurpose in question and which is generally about 0.001- percent, andpreferably 0.01-95 percent, by weight of the mixture.

Generally, the active compound is used in dosage amounts per unit areaof substantially between about l5-1,000g, preferably 40-600g, and mostpreferably 40-100g, per 10 ares, irrespective of the presence or absenceof such carrier vehicle.

The active compounds can also be used in accordance with the well-knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the sarne, via very effective atomizing equipment in finelydivided form, e. g. average particle diameter of from 50-100 microns; oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-16 fluidounces/acre, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95 percent by weight of theactive compound, or even the percent active substance alone, e.g. about20-100 percent by weight of the active compound.

In particular, the present invention contemplates methods of selectivelykilling, combating or controlling fungi, which comprise applying to atleast one of (a) such fungi and (b) their habitat, i.e. the locus to beprotected, a fungicidally efiective or toxic amount of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner, for instance by spraying, atornizing,vaporizing, scattering, dusting, watering, sprinkling, pouring,dressing, via incrustation; and the like.

Significantly, the fungicidal compositions of the present invention canbe applied for example by spraying a dust formulation directly ontostems and leaves of plants; or by using the formulation as aseed-dressing; by spraying an emulsifiable concentrate, diluted withwater, etc. to a desirable concentration, onto stems and leaves ofplants; by suspending a wettable powder in of the particular activecompound utilized in admixture with the carrier vehicle will depend uponthe intended application, the purpose for which the active compound isused, and the like. Therefore, in special cases, it is possible to goabove or below the aforementioned concentration ranges and dosageamounts per unitarea.

The following illustrate, without limitation, examples of formulationswhich may be used in accordance with the present invention:

FORMULATION A Fifteen parts of instant compound (1), 80 parts of amixture of diatomaceous earth and kaolin (1:5) and 5 parts of theemulsifier Runox (trade name of the product of Toho Kagaku Kogyo K.K.,Japan: polyoxyethylenealkylarylether) are formulated into a wettablepowder by crushing mixing. It is diluted with water at the concentrationof l to 300 500 and applied by spraying to the phytopathogenic fungiand/or their habitat.

FORMULATION B Thirty parts of instant compound (3), 30 parts of xyleneand 30 parts of Kawakazol (trade name of the product of Kawasaki KaseiKogyo K.K., Japan: aromatic hydrocarbons of high boiling point) andparts of the emulsifier Sorpol (trade name of the product of Toho KagakuKogyo K.K., Japan; polyoxyethylenealkylarylether) are formulated into anemulsifiable concentrate by mixing and stirring. It is diluted withwater at the concentration of l to 1,000 and applied by spraying to thephytopathogenic fungi and/or their habitat.

FORMULATION C Two parts of instant compound (4) and 98 parts of amixture of talc and clay (3:1) are formulated into a dust by crushingand mixing. It is applied as is by dusting to the phytopathogenic fungiand/or their habitat.

FORMULATION D "iir?fir1 iciili1ifivafl of the particular new compoundsof the present invention is illustrated, without limitation, by thefollowing Examples:

EXAMPLE 1 Piricularia test:

liquid preparation of active compound Test method: compound 1 part byweight acetone 0.05 part by weight sodium oleate Liquid preparation ofactive Solvent:

Dispersing agent:

Other additive:

Water:

0.2 part by weight gelatin 7 98.75 parts by weight.

The amount of the particular active compound required for the desiredconcentration of such active compound in the spray liquor is mixed withthe stated amount of solvent, and the resulting concentrate is dilutedwith the stated amount of water containing the stated additive.

(i) Test for preventive effect:

Thirty rice plants about 14 days old are sprayed with the spray liquorcontaining the given active compound until dripping wet. The plantsremain in a greenhouse at a temperature of 22 to 24C. and at a relativeatmospheric humidity of about percent until they are dry. Such plantsare then inoculated with'an aqueous suspension of 100,000 to 200,000spores/ml. of Piricularia oryzae and placed in a chamber at 24 26C andpercent relative atmospheric humidity.

Five days after inoculation, the infestation of all the leaves presentat the time of inoculation is determined as a percentage of theuntreated but also inoculated control plants. 0% means no infestation;100 percent means that the infestation is exactly as great as in thecase of the control plants.

(ii) Test for curative effect:

In the above described test, which uses a liquid preparation of theparticular active compound, the curative effect in addition to theprotective effect of the compounds is also determined. The test forcurative effect differs from the test procedure described above (whichonly provides evidence of the protective effect) insofar as the activecompounds are applied not before, but only 16 hours after, inoculation.Compounds which show an activity when the test is conducted in thismanner are in a position to kill the fungus after infec-' tion andthereby to exercise a curative action.

The particular active compounds tested, their concentrations and theresults obtained can be seen from the following Table 1:

TABLE 1 Test results of fungicidal eflect; against rice blast(Piricularia oryzae) Concentration of Infestation Infestation active(attack rate) (attack rate) compound in protective in curative Activecompound in percent efiect test effect test Known compound (comparison):

(A).. C II -O O 0.05 0 58 Present compounds; H

TAB LE 1- Continued (Piricularia or war) Concentration of InfestationInfestation netivn (attack rate) (attack mtu) compound in protective incurntivu Active compound in percent oilect test oiloot tnst (151)..-. I1H3 w 005 v 0 CH3CH2-CCIIz-OP-S Ha (211 5- S 0. 025 0 H6 (22 CHCHCHz-CHO\fi 0. 05 0 17 H3 H3 "P-SFQ-Ci CH (E(l3H0PSCl lHa CH3 62115-3O. 015 0 75 (18 CH -CHCH2CH-O O 0.05 0 0 I ll CH; II; IS-- C2II5-S 0.025 0 42 (191).... GIL-4 O 0.05 O 25 I ll 0. 025 0 CHs-CCHOPS- CH H; IC2H S (20 CH3 0 O. 05 0 0 I ll 0. 025 0 0 CH -C(|1H-0-P S H CH l CHa-S(21 CH3 0 0. 05 0 0 I' ll 0. 025 0 100 CH3C-(|JH-O-PS Cl CH3 CH3 CH3SCH3 0 0. 05 0 0 I H 0. 025 0 0 (231) CHa--OH- ICOHzO-1|S Cl CH3 CH -S(16 O S-CHs 0.05 0 0. 025 0 EXAMPLE 2 Test against plant pathogens (Agardilution method) The particular active compound is mixed in an agarculture medium of potato to form the desired concentration of activecompound therein. After the medium is poured into Petri dishes of 9 cmin diameter and coagulated, the same are inoculated with thecorresponding plant pathogens. Standard Petri dishes to which the activecompound of Zineb (zinc-ethylene bis-dithiocarbamate) preparations arenot added are also set up. After having been cultured at 27C for 4 days,the growth condition of the plant pathogens is investigated and theconcentration of the active compound (in ppm) for growth inhibition isdetermined.

The particular active compounds tested and the results obtained (i.e.the concentraion in ppm for growth inhibition) can be seen from thefollowing Table 2.

Fifty parts of test compound, 30 parts of xylene and parts of emulsifier(polyoxyethylenealkylarylether) are mixed and stirred to formemulsifiable concentrates. It is diluted with water at theconcentrationof l to 300 and soaked in an amount of 500 g per 10 a of the activecompound into the soil of pots of 12 cm in diameter in which paddy rice(Wase-Asahi) has been cultivated. After one day, an aqueous suspensionof 100,000 to 200,000 spores/ml. of rice blast pathogen (Piriculariaoryzae) is sprayed onto the rice plants of the so-soaked (i.e. treatedsoil) pots for the purpose of inoculation. The inoculated rice plantsare then kept in the greenhouse for 7 days, and the number of diseasedspots of rice blast, i.e. infestation, is investigated.

The particular active compounds tested and the results obtained can beseen from the following Table 3.

TABLE 3 Test results of fungicidal effect against rice blast (Soilapplication) ethyl-S-phenylphosphorodithiolate The following furtherexamples illustrate, without limitation, the process for producing theparticular new compounds of the present invention.

TABLE Z-Continued Test results of fungicidal effect against variousplant pathogens (Agar dilution method) I Pirz'cularia CochlzobolusPellicularia Alternaria Elsinoe Active Compound oryzae miyabeanussasskii kikuchiana ampelina No. (rice), (rice) ce), (p (g pe). p.p.m.p.p.m. p.p.m. p.p.m. p.p.m.

50 W 100 100 100 50 100 100 100 100 25 50 100 50 50 50 100 100 100 10050 100 100 100 100 100 100 100 100 100 (82) v 100 100 100 100 100 Zlneb(standard) 50 200 100 200 200 NOTE. Compounds of invention havecorresponding numbers to those of Table 1 above and Table 3 below, asthe casemay be. H V wflwfiw 4 W EXAMPLE 3 Test against rice blast/(Piricularia oryzae) [Soil appli- 2, 0 8-013, cation] Q JL/ Test method:

Eleven g of thiophenol and 10 g of triethylamine are dissolved in 200 mlof benzene. To this solution, 23 g of O( 1,3-dimethyl-butyl)-S-methyl-thiolphosphoryl chloride are added dropwise while cooling.After the addition, the mixture is stirred'for 1 hour at room temi.e. O(l,3-dimethyl-butyl)-S-methyl-Sfphenyldithiolphosphoric acid ester, areobtained.

Analysis S P Calculated: 21.0% 10.2% Found: 21.4% 10.3%

According to the same procedure as noted above,

. when O-(iso-butyl)-S-methyl-thiolphosphoryl chloride,

O-(sec-butyl)-S-ethyl-thiolphosphoryl chloride, '0-(sec-butyl)-S-n-propyl-thiolphosphoryl chloride, O( lmethyl-heptyl)-S-ethyl-thiol-phosphoryl chloride and O( l,2,2-trimethyl-propyl )-S-methylthiolphosphoryl chloride, respectively,is used instead of O-(l,3-

dimethyl-butyl)-S-methyl-thiolphosphoryl chloride, the correspondingO-alkyl-S-alkyl-S-phenylphosphorodithiolate is obtained:

( l O(iso-butyl)-S-methyl-Sphenylphosphorodithiolate (3O-(sec-butyl)-S-ethyl-S-phenylphosphorodithiolate (26O(sec-butyl)-S-n-propyl-S-phenylphosphorodithiolate (8 O(l-methyl-heptyl )-S-ethyl-S-phenylphosphorodithiolate (20 O(1,2,2-trimethyl-propyl )-S-methyl-S-phenylphosphorodithiolate Thesecompounds significantly have a similar fun gicidal activity to that ofcompound (2).

sodium sulfate. Upon distilling off the ether, 27 g of pale yellowishoily O-( l ,B-dimethyl-butyl)-S-methyl-S(4-chloro-phenyl)-phosphorodithiolate, i.e. O-(1,3-dimethyl-butyl)-S-methyl-S-(4'-chloro-phenyl)- dithiolphosphoric acidester, are obtained.

Ha Ha 21: 16.7 g of the sodium salt of 4-chloro-thiophenol are 15:70 Pdissolved in 200 ml of methyl ethyl ketone.' To this 335331 18.9% 9.2%solution, 23 g of O-( l,3-dimethyl-butyl)-S-methyl- Found 183% 89%thiolphosphoryl chloride are added dropwise while stirring. The mixtureis stirred for 1 hour at room temperature and for a further 8 hours at atemperature of 60C to complete the reaction. The inorganic salt formedis separated by filtration. The methyl ethyl ketone is distilled off andthe residue is dissolved in ether. 'The resulting ether solution iswashed with a 1 percent aqueous solution of sodium carbonate andthereafter with water, and is then dehydrated over anhydrous Accordingto the same procedure as noted above, when the sodium salt of4-methyl-thiophenol is used instead of the sodium salt ,of4-chlor0-thiophenol, the non-distillable pale yellowish oilyO-(1,3-dimethyl-butyl)-S-methyl-S-(4-methyl-phenyl)-phosphorodithiolate(27;), which has a similarfungicidal activity to that of compound 16 isobtained at l60C/0.1 mm Hg.

The following Table 3 illustrates appropriate data for typical compoundsaccording to the present invention.

TABLE4 Compound Physical No. Structural formula property (24) O S-OH; 11=L5582 ll/ S l) 0(|JIIC1I2CHCII:

CH3 CH:

(13) O S CH3 nD =li5730 H/ SP O-CH2CIICH3 O S-OzH nn =l.5622

O-CH-CHz-OHa (16 (H)/SCHa nn =1.5510

OCl'[CHs(|3HCl-Is CH CH;

(43) O S-OIIg I m =1.5764

O-CHz-CIJHCHa (242) SC II ls0 Oil.

()CHz-CHCH:|

1 (mi (251) (H) S( I.I 1 Oil.

cm-si O--Cll2(|JII-CII.1 CIIJ s-cmi on. 01ns-v o-omc1rcm 3) O S-CaHr,Oil.

()-(lg|l17-ll 'i-Cgll (m,

Physical p op y Compound N0.

Structural formula S-CII;

S-Czlla (IJz) These compounds may be designated: 2 O-( l,3-dimethyl-butyl )-S-methyl-S-phenylphosphorodithiolate lO-iso-butyl-S-methyl-S-phenylphosphorodithiolate (3O-sec-butyl-S-ethyl-S-phenyl-phosphorodithiolate 16 O-( 1,3-dimethyl-butyl)-S-methyl-S-(4-ch1orophenyD-phosphotodithiolate 4O-iso-butyl-S-methyl-S-( 4-chloro-phenyl)- phosphorodithiolate (24O-iso-butyl-S-is0-propyl-S-phenylphosphorodithiolate (25O-iso-butyl-S-methyl-S-(4-methyl-phenyl)- phosphorodithiolate I (6O-iso-butyl-S-ethyl-S-(4-methyl-phenyl)- phosphorodithiolate 7On-octyl-S-ethyl-S-phenyl-phosphorodithiolate 8 O-(1-methyl-hexyl)-S-et.hyl-S phenylphos; norodithiolate (9 i l2-ethyl-butyl )-S-methyl-S-( 4 chlor0-phenyl)-pnosphorodithiolate 10)O-(Z-ethyl-butyl)-S-ethyl-S-(4-chloro-phenyl)- phosphoro-dithiolate 1 lO-(2-ethyl-butyl)-S-ethyl-S-phenylphosphorodithiolate 12 )O-( 2-ethyl-butyl )-S-methyl-S-phenylphosphorodithiolate 13)O(2,2-dimethyl-butyl)-S-methyl-S-phenylphosphorodithiolate l 4 )O-(2,2-dimethyl-butyl )-S-ethyl-S-( 4-chlorophenyl)-phosphorodithiolate I15 )O-(2,2-dimethyl-butyl)-S-ethyl-S-phenylphosphorodithiolate 22 )O- l,3-dimethyl-butyl)-S-ethyl-S-(4-chlorophenyl)-phosphorodithiolate 17)O-( 1,2,2-trimethyl-propyl)-S-ethyl-S-(4-chloro-phenyl)-phosphorodithiolate 1 8 )O-(1,3-dimethyl-butyl)-S-ethyl-S-phenylphosphorodithiolate 19 )O-( 1,2,2-trimethyl-propyl)-S-ethyl-S-phenylphosphorodithiolate 20 O-( l,2,2-trimethyl-propyl )-S-methyl-S-phenylphosphorodithiolate (21O-(1,2,2-trimethyl-propyl)-S-methyl-S-(4-chloro-phenyl)-phosphorodithiolate v 5 O-sec.-butyl-S-ethyl-S-(4-chloro-phenyl)- phosphorodithiolate 23 O-( 2,2-dimethyl-butyl)-S-methyl-S-(4-chlorophenyl )phosphorodithiolate H v It will berealized by the artisan that all of .the foregoing compoundscontemplated by the present invention possess the desired strongfungicidal properties, with regard to a broad spectrum of activity, aswell as a comparatively low toxicity toward wann-bloqded 1 :eatures inwhich R is alkyl of one-three carbon atoms, R is selected from the groupconsisting of branched chain alkyl of four-eight carbon atoms andstraight chain alkyl of seven-eight carbon atoms, and X is selected fromthe group consisting of hydrogen and methyl.

2. Compound according to claim 1 wherein such compound isO-iso-butyl-S-methyl-S-phenylphosphorodithiolate.

3. Compound according to claim 1 wherein such compound isO-sec-butyl-S-ethyl-S-phenylphosphorodithiolate.

4. Compound according to claim 1 wherein such compound isO-sec.-butyl-S-ethyl-S-(4-chloro-phenyl)- phosphorodithiolate.

5. Compound according to claim 1 wherein such compound isO-(1,S-dimethyl-butyl)-S-methyl-S-phenyl-phosphorodithiolate.

6. Compound according to claim 1 wherein such compound isO(1,3-dimethyl-butyl)-S-ethyl-S-phenylphosphorodithiolate.

7. Compound according to claim 1 wherein such compound isO-(2,2-dimethyl-butyl)-S-methyl-S-phenyl-phosphorodithiolate.

8. Compound according to claim 1 wherein such compound isO-(2,2-dimethyl-butyl)-S-ethyl-S-phenylphosphorodithiolate.

9. Compound according to claim 1 wherein such compound isO-(Z-ethyl-butyl)-S-methyl-S-phenylphosphorodithiolate.

10. Compound according to claim 1 wherein such compound isO-(Z-ethyl-butyl)-S-ethyl-S-phenylphosphorodithiolate.

11. Compound according to claim 1 wherein such compound isO-(1,2,2-trimethyl-propyl)-S-methyl-S- phenyl-phosphorodithiolate.

UNITED S'IA'UCS IA'IICN'I (n-x-m'c CERTIFICATE OF CQRRECTION Patent NO.3,686,369 Dated August 22, 1972 Inventor(s) Hellmutt Hoffmann et al Itis certified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below: 7

Col. 2 line 61 "methyl, 1-4 and iso-propyl, should be methyl', ethyl,

nand iso-propyl,

Col. 3, lirie 37 "O-i-methyl-" should be O--l-methyl-- Col. 4 line 3Col. 9, Compound No. 5

" should be P' Col. 9 Compound No. 7

n n 4 0-c H should be 0 0 3 n Inventor(s UNHIIU S'IA'lilS PA'IF'ZN'IOFFICE CER'HIH(JATE 0F CORREQTKON Patent No. 3 686, 69 Dated August 221972 Hellmu tt Hoffmann et a1 It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Col. 9, Compount No. 9

IICH

Col. 10, Compound 12 omit the second "0.025 o o" Col. 12 Com ound 17"0.015" should be "10.025

Col. 12 Table 2 sesskii shonld be Q- Pel lic ularia sasakii" 7 Col. 12,Table 2 Under heading "Els inol a the second number, "40" should be 50UNI'IICI) S'lA'EICS PA'II'JNT (incmm CBERT?E IC/HE OF (IURRE I'llONPatent No. 3 686,369 Dated August 22 l972 Inventor(s) Hellmutl: Hoffmannet al 3 It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

C01. 13 Table 2 Column heading "Pellicularia sasskii" should bePellicularia sasakii Col. 1 line 36 .S-phenyl-dithiolphosphoric shouldbe -S-phenylphosphorodithiolate Col. l6 Compound 2 it Under "PhysicalProperty" "ni 1.5582" should be 21 n 1.5528 Col. 1g, Comrgund 16 "CH-CH-CH Should be -CH -CH-CH I I 3 CH f PC4050 ($69) USCOMM-DC 60376-P69Patent No. 9 Dated August 22, 1972 Inventor(s) Hellmutt Hoffmann et a1 4It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Col. 17, Compound 23 (EH v 1H -C-CH should be -C-CH Col. 20 line 20"one-three" should be one-two Col. 20, line 22 "four-eight" should befour-six (SEAL) Attest:

EDWARD M.,FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents IRM PO-IOSO (10-69) USCOMM-DC 6037 6-P69

2. Compound according to claim 1 wherein such compound isO-iso-butyl-S-methyl-S-phenyl-phosphorodithiolate.
 3. Compound accordingto claim 1 wherein such compound isO-sec-butyl-S-ethyl-S-phenyl-phosphorodithiolate.
 4. Compound accordingto claim 1 wherein such compound isO-sec.-butyl-S-ethyl-S-(4-chloro-phenyl)-phosphorodithiolate. 5.Compound according to claim 1 wherein such compound is O-(1,3-dimethyl-butyl)-S-methyl-S-phenyl-phosphorodithiolate.
 6. Compoundaccording to claim 1 wherein such compound is O-(1,3-dimethyl-butyl)-S-ethyl-S-phenyl-phosphorodithiolate.
 7. Compoundaccording to claim 1 wherein such compound is O-(2,2-dimethyl-butyl)-S-methyl-S-phenyl-phosphorodithiolate.
 8. Compoundaccording to claim 1 wherein such compound is O-(2,2-dimethyl-butyl)-S-ethyl-S-phEnyl-phosphorodithiolate.
 9. Compoundaccording to claim 1 wherein such compound isO-(2-ethyl-butyl)-S-methyl-S-phenyl-phosphorodithiolate.
 10. Compoundaccording to claim 1 wherein such compound isO-(2-ethyl-butyl)-S-ethyl-S-phenyl-phosphorodithiolate.
 11. Compoundaccording to claim 1 wherein such compound is O-(1,2,2-trimethyl-propyl)-S-methyl-S-phenyl-phosphorodithiolate.